JPH0320485A - Method for rinsing metallic material - Google Patents
Method for rinsing metallic materialInfo
- Publication number
- JPH0320485A JPH0320485A JP15494789A JP15494789A JPH0320485A JP H0320485 A JPH0320485 A JP H0320485A JP 15494789 A JP15494789 A JP 15494789A JP 15494789 A JP15494789 A JP 15494789A JP H0320485 A JPH0320485 A JP H0320485A
- Authority
- JP
- Japan
- Prior art keywords
- rinsing
- rinse
- sheet
- discoloration
- equipment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000007769 metal material Substances 0.000 title claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005554 pickling Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims description 32
- 230000007423 decrease Effects 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000012487 rinsing solution Substances 0.000 claims description 7
- 238000002845 discoloration Methods 0.000 abstract description 29
- 229910000831 Steel Inorganic materials 0.000 abstract description 28
- 239000010959 steel Substances 0.000 abstract description 28
- 238000005406 washing Methods 0.000 abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004140 cleaning Methods 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 230000006866 deterioration Effects 0.000 abstract 2
- 239000013505 freshwater Substances 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 13
- 239000010949 copper Substances 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 11
- 238000011144 upstream manufacturing Methods 0.000 description 7
- 229960004887 ferric hydroxide Drugs 0.000 description 6
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 229960002089 ferrous chloride Drugs 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 ferrous metals Chemical class 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical class [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004649 discoloration prevention Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G3/00—Apparatus for cleaning or pickling metallic material
- C23G3/02—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
- C23G3/027—Associated apparatus, e.g. for pretreating or after-treating
- C23G3/029—Associated apparatus, e.g. for pretreating or after-treating for removing the pickling fluid from the objects
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
【発明の詳細な説明】
［ａ業上の利用分野］
本発明は酸洗処理された金属材料のリンス方法に関し、
特に金属材料を連続的に酸洗しリンス処理していく際に
おいて、ライントラブル等により金属材料の走行速度が
低下したり或は停止した場合に生ずる金属材料の変色を
防止する方法に関するものである。尚木発明の対象とな
る金属材料としては、各種合金鋼やＡＩ，Ｃｕ等の非鉄
金属あるいはこれらの合金等種々の金属材料が挙げられ
、その形状も帯状、棒状、線状等様々のものがあるが、
以下の説明では銅帯を代表的にとり上げて説明する．
［従来の技術］
銅帯の連続生産に当たっては、熱間圧延や玲間圧延工程
あるいは歪取り焼鈍工程等で生成する表面の酸化スケー
ルを除去して正常化するため、最終段階で酸洗による脱
スケール処理と、酸洗液除去のためのリンス処理が行な
われる。たとえば第５図は通常のリンス処理設備を例示
するもので、リンス処理設備３は、酸洗設備２の後方に
鋼帯１の走行方向に沿って複数の散水リンス部３ａ，３
ｂ，・・・３ｙ，３ｚを直列に配設してなり、酸洗設備
２から出た鋼ｆ１は、各散水リンス部３ａ，３ｂ，・・
・において、各受槽４ａ，４ｂ，・・・より循環ポンブ
Ｐを経て各散水ノズル５ａ，５ｂ，・・・から噴出され
る洗浄水によって順次リンス処理された後、乾燥装置６
ヤ乾燥して巻取られる．このリンス処理設備３において
、洗浄水は最下流側リンス部３ｚの循環ラインもしくは
受槽４ｚへ供給され、該リンス部３Ｚの受禮４ｚからオ
ーバーフローした洗浄水はその上流側リンス部３ｙの受
槽４ｙへ送られ、これを順次繰り返した後最上流側リン
ス部３ａの受槽４ａもしくは循環ラインから逐次抜き出
される．この間、鋼帯１表面の酸洗液（最も多用されて
いるのは塩酸）付着量は、最上流側リンス部３ａより下
流側になるにつれて減少し、最下流側リンス部３ｚでは
実質的に零となる。また最上流側リンス部３ａでは多量
の酸洗液が除去されるため、受槽４ａ内の洗浄液ｐ｝Ｉ
が最も低くなり、下流側リンス部になるほど該リンス部
で洗浄除去される酸洗液絶対量が少なくなるため、各受
槽の洗浄液ｐ｝ｌは徐々に中性に近づいてくる。[Detailed description of the invention] [A field of application] The present invention relates to a method for rinsing pickled metal materials,
In particular, it relates to a method for preventing discoloration of metal materials that occurs when the running speed of the metal material decreases or stops due to line trouble, etc. when continuously pickling and rinsing the metal material. . The metal materials that are the object of Naoki's invention include various metal materials such as various alloy steels, non-ferrous metals such as AI and Cu, and alloys of these metals, and their shapes include various shapes such as strips, rods, and wires. Yes, but
In the following explanation, we will take up the copper belt as a representative example. [Conventional technology] In the continuous production of copper strips, in order to remove and normalize the oxidized scale on the surface that is generated during hot rolling, rolling, stress relief annealing, etc., decomposition by pickling is carried out in the final stage. Scale treatment and rinsing treatment to remove the pickling solution are performed. For example, FIG. 5 illustrates a normal rinsing equipment, in which the rinsing equipment 3 includes a plurality of water spray rinsing parts 3a, 3 along the running direction of the steel strip 1 behind the pickling equipment 2.
b,...3y, 3z are arranged in series, and the steel f1 coming out of the pickling equipment 2 is connected to each water spray rinsing section 3a, 3b,...
In ・, after being rinsed in sequence with washing water spouted from each water spray nozzle 5a, 5b, . . . via a circulation pump P from each receiving tank 4a, 4b, .
It is dried and rolled up. In this rinsing treatment equipment 3, washing water is supplied to the circulation line or receiving tank 4z of the most downstream rinsing section 3z, and the washing water overflowing from the receiving tank 4z of the rinsing section 3Z is sent to the receiving tank 4y of the upstream rinsing section 3y. After repeating this process, they are sequentially extracted from the receiving tank 4a of the most upstream rinsing section 3a or from the circulation line. During this period, the amount of pickling solution (the most commonly used is hydrochloric acid) attached to the surface of the steel strip 1 decreases as it moves downstream from the most upstream rinse section 3a, and reaches substantially zero at the most downstream rinse section 3z. becomes. In addition, since a large amount of pickling liquid is removed in the most upstream rinsing section 3a, the cleaning liquid p}I in the receiving tank 4a
is the lowest, and the absolute amount of pickling solution washed and removed in the downstream rinsing section decreases, so the cleaning solution p}l in each receiving tank gradually approaches neutrality.
［発明が解決しようとする課題］
第５図に示した様なリンス処理設備によるリンス効果は
、鋼帯１の連続生産ラインが順調に稼動し鋼帯１が一定
の速度で走行している限り何ら問題を生ずることはない
。ところが連続生産ラインの一部（熱延もしくは冷延工
程や焼鈍工程、酸洗工程等）でトラブルが生じて、リン
ス処理設備における銅帯の走行速度が低下したり停止す
ると、次の様な問題が生じてくる．
即ちリンス処理設備の特に上流側では、前述の如く酸洗
液がまだ完全社除去されておらず、各リンス部で循環供
給される洗浄水はかなり強い酸性を示しているので、こ
の様な酸性水が付着したままの状態で銅帯の走行が停止
すると、後述する様な反応により銅帯表面が黄色、黒色
、赤色等に変色し品質が著しく損なわれる．
そこでこうした問題を回避するため、銅帯の走行速度が
低下したり停止したときは、リンス処理設備全体の受糟
に大量の洗浄水を供給して洗浄水のｐ｝Ｉを中性にする
手段がとられている。ところがこの手段では、この時点
でリンス処理設備から排出される酸洗排水等の量が急増
するため、排出処理設備にかかる負荷が著しく増大する
．従ってリンス処理設備に付設される排水処理設備とし
ては、こうした不測の事態も考慮したうえで大量の排液
を処理し得る大規模な排水処理設備を設けておかねばな
らず、設備費が高騰する．しかもリンス処理設備におけ
るすべてのリンス部に上記の処理を施さなければならな
いので、清浄水の使用量増大に伴なうコストアップも軽
視できない．本発明はこの様な事情に着目してなされた
ものであって、その目的は、リンス処理設備を通過する
銅帯の走行速度が低下し或は停止した場合でも、前述の
様な問題を生ずることなく銅帯の変色を確実に防止する
ことのできる方法を提供しようとするものである。[Problems to be Solved by the Invention] The rinsing effect of the rinsing treatment equipment as shown in FIG. No problems will occur. However, if a problem occurs in a part of the continuous production line (hot rolling or cold rolling process, annealing process, pickling process, etc.) and the running speed of the copper strip in the rinsing equipment decreases or stops, the following problems may occur: arises. In other words, especially on the upstream side of the rinsing treatment equipment, the pickling liquid has not yet been completely removed as described above, and the cleaning water that is circulated and supplied to each rinsing section is quite acidic. If the copper strip stops running with water still adhering to it, the surface of the copper strip will change color to yellow, black, red, etc. due to the reaction described below, resulting in a significant loss of quality. Therefore, in order to avoid such problems, when the traveling speed of the copper strip decreases or stops, a means is provided to neutralize p}I of the washing water by supplying a large amount of washing water to the drain of the entire rinsing treatment facility. is taken. However, with this method, the amount of pickling wastewater etc. discharged from the rinsing treatment equipment increases rapidly at this point, resulting in a significant increase in the load on the wastewater treatment equipment. Therefore, the wastewater treatment equipment attached to the rinsing treatment equipment must be large-scale wastewater treatment equipment capable of treating a large amount of wastewater, taking into consideration such unforeseen circumstances, and equipment costs will rise. ．． Moreover, since all the rinsing parts in the rinsing treatment equipment must be subjected to the above treatment, the cost increase due to the increased amount of clean water used cannot be ignored. The present invention has been made with attention to such circumstances, and its purpose is to prevent the above-mentioned problems from occurring even when the traveling speed of the copper strip passing through the rinsing treatment equipment decreases or stops. The object of the present invention is to provide a method that can reliably prevent discoloration of copper strips without causing any damage.
［課題を解決するための千段］
上記課題を解決することのできた本発明に係るリンス方
法の構成は、酸洗後の金属材料を数段階に分けて形成し
たリンス設備を順次通過させることによってリンスして
いくに当たり、上記通過速度が低下したときには、リン
ス液のｐＨ値が１．５〜４．０の範囲内の値を示すリン
ス設備におけるリンス液（洗浄液）に水を補給し、ある
いは該リンス液の温度を低下させ、もしくは該リンス液
中の酸素濃度を低下させるところに要旨を有するもので
ある．
［作用及び実施例］
本発明者らはこれまでの経験で、前述の様な不測の事態
が生じたときに見られる変色が、リンス処理設備内にお
ける特定の部位で集中的に発生することを確かめている
。またリンス処理設備における洗浄水のｐ｝ｌは、最上
流ｆｆＩＩＪリンス部で最も低く、下流側リンス部にな
るにつれて中性に近づいてくることは先に述べた通りで
ある。そこで鋼帯が変色するか否かは、洗浄水のｐ｝Ｉ
によって影響を受けるのではないかと考え、次の方法で
洗浄液のｐＨと変色の関係を調べた。[A Thousand Steps to Solve the Problems] The configuration of the rinsing method according to the present invention that can solve the above problems is that the metal material after pickling is sequentially passed through rinsing equipment formed in several stages. During rinsing, if the above-mentioned passing speed decreases, replenish water to the rinsing liquid (cleaning liquid) in the rinsing equipment where the pH value of the rinsing liquid is within the range of 1.5 to 4.0, or The gist is to lower the temperature of the rinsing liquid or to lower the oxygen concentration in the rinsing liquid. [Operations and Examples] The present inventors have learned from past experience that the discoloration seen when the above-mentioned unexpected situation occurs occurs concentratedly in a specific part of the rinsing equipment. I'm making sure. Further, as described above, p}l of the washing water in the rinsing treatment equipment is lowest at the most upstream ffIIJ rinsing section, and approaches neutrality toward the downstream rinsing section. Whether the steel strip discolors or not depends on the washing water p}I
We thought that the relationship between the pH of the cleaning solution and discoloration was investigated using the following method.
（実験法）
（１）試験条件
・リンス液：既設リンス処理設備における最上流側から
４番目のリンス部の
循環液を水で希釈して使用
・リンス液水’ｉｔ：ｐＨ・・・１〜７、温度・・・３
０，５０．７０ （’ｅ） 、流量・・・１０〜３３（
ＩＬ／分）
・リンス時間：５〜３００（秒）
・ノズルー鋼板間距１１： １００ 〜２８０（１１１
１１１）（２）試験法
塩酸で脱スケールした鋼板を水洗一温
水洗浄一水洗の後乾燥し冷却したものを供試鋼板とし、
これを２０ｇ／１濃度のＦｅＣｌ２水溶液に浸漬してか
ら所定のリンス液でリンス処理を行ない、乾燥後鋼板表
面の変色状態を調べる。(Experimental method) (1) Test conditions - Rinse liquid: use the circulating liquid in the fourth rinsing section from the most upstream side of the existing rinsing treatment equipment diluted with water - Rinse liquid water'it: pH...1~ 7. Temperature...3
0.50.70 ('e), flow rate...10~33 (
IL/min) ・Rinse time: 5 to 300 (seconds) ・Nozzle distance between steel plates 11: 100 to 280 (111
111) (2) Test method A steel plate that has been descaled with hydrochloric acid is washed with water, washed with hot water, dried and cooled after washing, and is used as a test steel plate.
This was immersed in an aqueous FeCl2 solution with a concentration of 20 g/1, then rinsed with a predetermined rinsing liquid, and after drying, the state of discoloration on the surface of the steel plate was examined.
（３）変色の評価法
上記（２）で得た鋼板の表面の色調をミノルタ社製の色
度計により測定し、３点測定の平均値として求める。(3) Evaluation method for discoloration The color tone of the surface of the steel plate obtained in the above (2) is measured using a color meter manufactured by Minolta, and the average value of the three-point measurements is determined.
Ｌ値：白一黒の明度
第１図はリンス液の温度を７０℃、リンス時間を６０秒
に設定し、リンス液のｐ｝ｌを変えた場合について鋼板
の変色状態を調べた結果を示したものである。L value: Brightness of black and white Figure 1 shows the results of examining the state of discoloration of the steel plate when the temperature of the rinsing liquid was set to 70°C, the rinsing time was set to 60 seconds, and the p}l of the rinsing liquid was changed. It is something that
この図からも明らかである様に、鋼板はリンス液のｐＨ
が１．５〜４．０の範囲で著しく変色し、このｐＨ域を
外れた場合は殆んど変色しない。As is clear from this figure, the steel plate is affected by the pH of the rinsing liquid.
The color changes significantly in the pH range of 1.5 to 4.0, and there is almost no color change outside this pH range.
こうした傾向を示す理由は次の様に考えることができる
．
即ち酸（｝ＩＣｊ２）洗を受けた鋼板の表面には、下記
の反応により生成した塩化第１鉄が付着しているが、
ＦｅＯ＋２ＨＣ角−＊ＦｅＣＩｌ２ ＋Ｈ２ ０こ
の塩化第１鉄は、第２図に示す如くリンス処理工程で水
酸化第２鉄に変化する。この水酸化第１鉄は非常に酸化
され易く、リンス液中の酸素により酸化されて水酸化第
２鉄に変わる．そしてこの水酸化第２鉄はｐｌ｛２．０
以上になると溶解度が著しく低下し、鋼板表面に析出し
てくるが、これが脱水されると酸化第２鉄に変化し着色
するものと思われる。The reason for this tendency can be considered as follows. That is, ferrous chloride produced by the following reaction is attached to the surface of the steel plate that has been washed with acid (}ICj2). As shown in the figure, it changes to ferric hydroxide during the rinsing process. This ferrous hydroxide is very easily oxidized and is oxidized by the oxygen in the rinse solution, turning into ferric hydroxide. And this ferric hydroxide is pl{2.0
If the temperature exceeds that level, the solubility decreases significantly and precipitation occurs on the surface of the steel sheet, but when this is dehydrated, it is thought to change to ferric oxide and become colored.
このとき、リンス液のｐＨが１．５未満である場合は、
鋼板表面に多量に存在する塩化第１鉄が水酸化第２鉄に
変化したとしても、ｐｌ｛が低いため該水酸化第２鉄の
析出が起こらず、その後の水洗で容易に除去されるため
鋼板の変色は起こりにくい。At this time, if the pH of the rinse solution is less than 1.5,
Even if ferrous chloride, which exists in large quantities on the surface of the steel sheet, changes to ferric hydroxide, the ferric hydroxide does not precipitate because the PL is low, and is easily removed by subsequent washing with water. Discoloration of steel plates is unlikely to occur.
一方、リンス液のｐＨが４．０を超える場合は、塩化第
１鉄の溶解速度が極めて遅く、そのため水酸化第１鉄の
生成、ひいてはその酸化によって生ずる水酸化第２鉄の
生戒が起こらず、その結果酸化第２鉄も生成しにくくな
って鋼板表面の変色が起こらなくなるものと思われる。On the other hand, if the pH of the rinsing solution exceeds 4.0, the dissolution rate of ferrous chloride is extremely slow, which prevents the production of ferrous hydroxide and, by extension, the oxidation of ferric hydroxide. As a result, it is thought that ferric oxide is also less likely to be produced and discoloration of the steel sheet surface does not occur.
即ち鋼板の変色を防止するには、第２図に示したＦｅＣ
１２−＊Ｆａ （ＯＨ）２−＊Ｆｅ （ＯＨ）３一Ｆｅ
２０，の反応をいずれかの段階で阻止して酸化第２鉄が
生成しない様な条件を与えてやればよく、リンス液のｐ
Ｈを１．５〜４．０の範囲外にコントロールするとその
条件が与えられ、鋼板の変色が防止されるものと思われ
る。In other words, in order to prevent discoloration of the steel plate, FeC shown in Fig.
12-*Fa (OH)2-*Fe (OH)3-Fe
It is sufficient to prevent the reaction in step 20 at any stage and provide conditions such that ferric oxide is not produced.
It is thought that if H is controlled outside the range of 1.5 to 4.0, such conditions will be provided and discoloration of the steel plate will be prevented.
また上記の変色反応の速度は温度およびリンス処理系の
酸素濃度によっても変わってくる。たとえば第３図は、
リンス液の温度を変えた場合のリンス時間（スプレー時
間）と変色状態の関係を示したグラフである．但し使用
したリンス液としては下記の通りである．
（リンス液）
Ｇ）Ｈ ：２．５
比重： ０．９９４ ｇ ／ ｍｌ
Ｈ Ｃ Ｊｌ ｆＡ度 ：ｏ．２ｇ／Ａ以下Ｆ ｅ
Ｃ Ｉｔ ２濃度：０．１９ｇ／ｊ２ＣＩＬ濃度
：２０４ｍｇ／ＩＬ
第３図からも明らかである様に、リンス液ｐＨが変色を
最も起こし易い２．５であっても、リンス液の温度を十
分に下げてやれば鋼板の変色は起こり難くなり、リンス
液を冷却することが変色防止の有効な手段となる．
また第４図は、リンス液のｐ｝ｌを２．５、温度を７０
度、流量を３ ３ １１ ／ｗｉｎ ，リンス時間を３
０秒または６０秒に設定し、リンス液中の酸素濃度を変
えた場合の変色状態を調べた結果を示したものである。The rate of the above-mentioned discoloration reaction also varies depending on the temperature and oxygen concentration of the rinsing system. For example, in Figure 3,
This is a graph showing the relationship between rinsing time (spray time) and discoloration state when the temperature of the rinsing liquid is changed. However, the rinsing liquid used is as follows. (Rinse liquid) G)H: 2.5 Specific gravity: 0.994 g/ml H C Jl fA degree: o. 2g/A or lessFe
C It 2 concentration: 0.19g/j2CIL concentration
:204mg/IL As is clear from Figure 3, even if the pH of the rinsing liquid is 2.5, which is the most likely to cause discoloration, if the temperature of the rinsing liquid is lowered sufficiently, discoloration of the steel plate will be less likely to occur. , cooling the rinse solution is an effective means of preventing discoloration. In addition, Figure 4 shows that the p}l of the rinse liquid is 2.5 and the temperature is 70.
degree, flow rate 3 3 11 /win, rinse time 3
This figure shows the results of examining the state of discoloration when the oxygen concentration in the rinse solution was set to 0 seconds or 60 seconds and the oxygen concentration in the rinse solution was changed.
この図からも明らかである様に、リンス液ｐＨが最も変
色を起こし易い２．５であり且つ比較的高温条件にある
場合でも、リンス液中の酸素濃度を十分に下げてやれば
前述の酸化反応が進行しにくくなり、鋼板の変色は抑え
られる．
本発明はこうした実験事実を基にしてなされたものであ
って、その具体的構成は、リンス処理設備における銅帯
の通過速度が低下しあるいは停止したときは、リンス液
のｐＨ値が１．５〜４．０の範囲内の値を示すリンス部
（即ち変色する可能性のある部分）だけに注目し、当該
リンス部だけに水を補給してリンス液のｐＨを４．０よ
り高い値Ｃするか、あるいは該リンス液を冷却し、もし
くは該リンス液の酸素濃度を低下させることとし、変色
の恐れのない他のリンス部については定常状態のリンス
条件をそのまま維持するものである。As is clear from this figure, even if the pH of the rinse solution is 2.5, which is the most likely to cause discoloration, and the condition is relatively high temperature, if the oxygen concentration in the rinse solution is sufficiently lowered, the above-mentioned oxidation can be prevented. This makes it difficult for the reaction to proceed, and the discoloration of the steel plate is suppressed. The present invention was made based on these experimental facts, and its specific configuration is such that when the passing speed of the copper strip in the rinsing treatment equipment decreases or stops, the pH value of the rinsing solution is 1.5. Focusing only on the rinsing area that shows a value within the range of ~4.0 (i.e., the area where there is a possibility of discoloration), replenish water only to that rinsing area to increase the pH of the rinsing solution to a value higher than 4.0 C. Alternatively, the rinsing liquid is cooled or the oxygen concentration of the rinsing liquid is lowered, and the steady-state rinsing conditions are maintained for other rinsing parts where there is no risk of discoloration.
その結果、リンス処理設備全体のリンス液に水を供給し
て変色を防止する従来法に比べると、本発明は該設備の
掻く一部だけに前述の処理を施すものであるからリンス
処理設備全体としての給水量は著しく抑えられ、排水処
理設備を８ｉ端に大規模化しておく必要もなくなる。尚
リンス処理設備においてリンス液のｐＨ値が１，５〜４
．０の範囲になる位置は、該リンス処理設備のリンス能
力や鋼帯の走行速度により変わってくるので、本発明を
実施するに当たっては定常稼動時における各リンス部の
リンス液ｐＨを予め測定しておき、そのｐＨが１．５〜
４．０の範囲となるリンス部を確認しておいて、Ｗ４ｖ
の走行速度が低下したり停止したときは当該リンス部だ
けに前述の変色防止処理を施せばよい．尚当該リンス部
の酸素濃度を下げる手段としては、たとえば当該リンス
部の檀内に窒素ガス等をバプリングして溶存酸素を放出
させる方法等を採用すればよい。また本発明を実施する
に当たっては前記３つの手段のうち１つを採用するだけ
で目的を達成することができるが、これらの手段を２つ
以上組合わせ、ｋとえば該当するリンス部に冷水を供給
してｐＨを高めつつ冷却する方法等を採用すれば、変色
を一層確実に阻止することができるので好ましい．
［発明の効果］
本発明は以上の様に構成されており、リンス処理設備内
はおける綱帯の走行速度が低下し或は停止したときは、
該リンス処理設備におけるリンス液ｐ｝Ｉが１．５〜４
．０の範囲の値を示すリンス部のみに前記した所定の処
理を施すだけで銅帯の変色を確実に阻止することができ
、リンス排液処理設備を小型化し得ると共に洗浄水の使
用量も低減することができ、またリンス処理設備の掻く
一部に所定の処理を施すだけであるから工程管理も容易
であるなど、実用に即した多大な利益を享受することが
できる。また本願発明は銅帯の連続リンス処理に限らず
、酸洗された様々の金属帯や板材、線材、管材、棒材の
リンス処理にも幅広く活用することができる。As a result, compared to the conventional method in which water is supplied to the rinsing liquid of the entire rinsing equipment to prevent discoloration, the present invention applies the above-mentioned treatment to only a portion of the rinsing equipment. The amount of water supplied is significantly reduced, and there is no need to increase the scale of wastewater treatment equipment to the 8i end. In addition, in the rinsing treatment equipment, the pH value of the rinsing liquid is 1.5 to 4.
．． The position in the 0 range varies depending on the rinsing capacity of the rinsing equipment and the running speed of the steel strip, so when implementing the present invention, the pH of the rinsing solution in each rinsing section during steady operation must be measured in advance. and the pH is 1.5~
Check the rinse part that falls within the range of W4v.
When the running speed of the vehicle decreases or the vehicle stops, the above-mentioned discoloration prevention treatment can be applied only to the relevant rinse section. As a means for lowering the oxygen concentration in the rinsing section, for example, a method may be employed in which nitrogen gas or the like is bubbled into the rinsing section to release dissolved oxygen. Furthermore, in carrying out the present invention, the object can be achieved by employing only one of the three means described above, but it is possible to combine two or more of these means, for example by pouring cold water into the relevant rinsing section. It is preferable to adopt a method of supplying and cooling while raising the pH, since discoloration can be more reliably prevented. [Effects of the Invention] The present invention is configured as described above, and when the running speed of the rope inside the rinsing equipment decreases or stops,
The rinsing liquid p}I in the rinsing treatment equipment is 1.5 to 4.
．． Discoloration of the copper strip can be reliably prevented by simply applying the above-mentioned predetermined treatment to only the rinsing part that shows a value in the 0 range, making it possible to downsize the rinsing liquid treatment equipment and reducing the amount of washing water used. Furthermore, since only a predetermined treatment is applied to a portion of the rinsing treatment equipment, process control is easy, and many practical benefits can be enjoyed. Further, the present invention is not limited to the continuous rinsing treatment of copper strips, but can be widely utilized for rinsing treatment of various pickled metal strips, plate materials, wire rods, tube materials, and bar materials.
第１図はリンス液のｐＨと鋼板の変色度の関係を示すグ
ラフ、第２図は鋼板の変色原因を示す化学変化の説明図
、第３図はリンス所要時間と変色度の関係を示すグラフ
、第４図はリンス液中の酸素濃度と変色度の関係を示す
グラフ、第５図はリンス処理設備を示す概略図である。
１・・・鋼！Ｆ ２・・・酸洗設備３・・・
リンス処理設備
３ ａ， ３ ｂ． −・・３ ｙ， ３ ｚ・・
・リンス部４ａ，４ｂ，−＝４７，４ｚ・・・受禮Ｐ・
・・循環ポンプ
５ａ．５ｂ，・・・５ｙ，５ｚ・・・噴射ノズル６・・
・乾燥設備Figure 1 is a graph showing the relationship between the pH of the rinsing liquid and the degree of discoloration of the steel plate, Figure 2 is an explanatory diagram of chemical changes that show the causes of discoloration of the steel plate, and Figure 3 is a graph showing the relationship between the required time for rinsing and the degree of discoloration. , FIG. 4 is a graph showing the relationship between the oxygen concentration in the rinsing liquid and the degree of discoloration, and FIG. 5 is a schematic diagram showing the rinsing treatment equipment. 1...Steel! F 2... Pickling equipment 3...
Rinse treatment equipment 3 a, 3 b. −・・3 y, 3 z・・
・Rinse parts 4a, 4b, -=47, 4z...Urei P・
...Circulation pump 5a. 5b,...5y,5z...Injection nozzle 6...
・Drying equipment
Claims (3)
ス設備を順次通過させることによってリンスしていくに
当たり、上記通過速度が低下したときには、リンス液の
ｐＨ値が１．５〜４．０の範囲内の値を示すリンス設備
におけるリンス液に水を補給することを特徴とする金属
材料のリンス方法。(1) When rinsing the metal material after pickling by sequentially passing it through a rinsing equipment formed in several stages, if the passing speed decreases, the pH value of the rinsing solution will be 1.5 to 4. 1. A method for rinsing a metal material, comprising replenishing water to a rinsing liquid in rinsing equipment that exhibits a value within the range of .0.
ス設備を順次通過させることによってリンスしていくに
当たり、上記通過速度が低下したときには、リンス液の
ｐＨ値が１．５〜４．０の範囲内の値を示すリンス設備
におけるリンス液の温度を低下させることを特徴とする
金属材料のリンス方法。(2) When rinsing the metal material after pickling by sequentially passing it through a rinsing equipment formed in several stages, when the above-mentioned passing speed decreases, the pH value of the rinsing solution is 1.5 to 4. 1. A method for rinsing metal materials, characterized by lowering the temperature of a rinsing liquid in rinsing equipment that exhibits a value within the range of .0.
ス設備を順次通過させることによってリンスしていくに
当たり、上記通過速度が低下したときには、リンス液の
ｐＨ値が１．５〜４．０の範囲内の値を示すリンス設備
におけるリンス液中の酸素濃度を低下させることを特徴
とする金属材料のリンス方法。(3) When rinsing the metal material after pickling by sequentially passing it through a rinsing equipment formed in several stages, when the above-mentioned passing speed decreases, the pH value of the rinsing solution is 1.5 to 4. A method for rinsing metal materials, characterized by reducing the oxygen concentration in a rinsing liquid in rinsing equipment, which exhibits a value within the range of .0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15494789A JPH0320485A (en) | 1989-06-16 | 1989-06-16 | Method for rinsing metallic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15494789A JPH0320485A (en) | 1989-06-16 | 1989-06-16 | Method for rinsing metallic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0320485A true JPH0320485A (en) | 1991-01-29 |
| JPH0541711B2 JPH0541711B2 (en) | 1993-06-24 |
Family
ID=15595399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15494789A Granted JPH0320485A (en) | 1989-06-16 | 1989-06-16 | Method for rinsing metallic material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0320485A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04346684A (en) * | 1991-05-22 | 1992-12-02 | Sumitomo Metal Ind Ltd | Discoloration preventing method and device for continuous pickling line |
| JPH05295570A (en) * | 1992-04-20 | 1993-11-09 | Japan Energy Corp | Surface treatment of copper and copper alloy |
| EP0595686A1 (en) * | 1992-10-19 | 1994-05-04 | Sollac | Process for pickling steel materials |
| WO2018173287A1 (en) | 2017-03-24 | 2018-09-27 | 新日鐵住金株式会社 | Method for manufacturing steel sheet |
| JP2022133914A (en) * | 2021-03-02 | 2022-09-14 | Ｊｆｅスチール株式会社 | Manufacturing method of steel strip and manufacturing facility |
-
1989
- 1989-06-16 JP JP15494789A patent/JPH0320485A/en active Granted
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04346684A (en) * | 1991-05-22 | 1992-12-02 | Sumitomo Metal Ind Ltd | Discoloration preventing method and device for continuous pickling line |
| JPH05295570A (en) * | 1992-04-20 | 1993-11-09 | Japan Energy Corp | Surface treatment of copper and copper alloy |
| EP0595686A1 (en) * | 1992-10-19 | 1994-05-04 | Sollac | Process for pickling steel materials |
| WO2018173287A1 (en) | 2017-03-24 | 2018-09-27 | 新日鐵住金株式会社 | Method for manufacturing steel sheet |
| KR20190091306A (en) | 2017-03-24 | 2019-08-05 | 닛폰세이테츠 가부시키가이샤 | Method of manufacturing steel sheet |
| US11401567B2 (en) | 2017-03-24 | 2022-08-02 | Nippon Steel Corporation | Manufacturing method of steel sheet |
| JP2022133914A (en) * | 2021-03-02 | 2022-09-14 | Ｊｆｅスチール株式会社 | Manufacturing method of steel strip and manufacturing facility |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0541711B2 (en) | 1993-06-24 |
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